Dyeing textile with a dye solution containing a copolymer of an alkyl siloxane and a polyaminoalkylsiloxane having at least 3 carbons in the alkyl chain



United States Patent 3,512,915 DYEING TEXTILE WITH A DYE SOLUTIONCONTAINING A COPOLYMER OF AN ALKYL SILOXANE AND A POLYAMINOALKYLSILOX-ANE HAVING AT LEAST 3 CARBONS IN THE ALKYL CHAIN John L. Speier,Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., acorporation of Michrgan No Drawing. Continuation-impart of applicationsSer. No. 753,115 and Ser. No. 753,153, both filed Aug. 4, 1958. Thisapplication May 13, 1960, Ser. No. 28,851

Int. Cl. D06p /08 US. Cl. 88 8 Claims ABSTRACT OF THE DISCLOSURE Cotton,linen, wood, wool, silk, and glass, acrylic, polyester, nylon, Vinyon,polyolefin, metallic, plastic coated metallic and metallic coatedplastic yarns are dyed with any dye in a dyebath containing a copolymerof a polyaminopropylsiloxane and an alkylsiloxane.

The present invention relates to an improved process for coloringtextile fibers.

This application is a continuation-in-part of copending applicationsSer. Nos. 753,115 and 753,153, both filed Aug. 4, 1958 (both nowabandoned after refiling the combined subject matter thereof as Ser. No.176,797, filed Mar. 1, 1962). The former is a continuation-in-part ofcopending application Ser. No. 723,991, filed Mar. 26, 1958 (issued asPat. No. 2,971,864 on Feb. 14, 1961) which is in turn acontinuation-in-part of the then copending application Ser. No. 704,343,filed Dec. 23, 1957 (now abandoned).

The textile dyeing art is a highly developed one, but there is a greatneed for improvement in the resistance of dyed textiles to fading fromlight, washing, dry clean ing, the atmosphere, or other color destroyingagents. The crocking of dyed fabrics (i.e., the undesirable property bywhich coloring matter rubs oii from a fabric onto another material) hasalso been an age-old problem.

Although special dyes and/or special techniques for particular textileshave been developed which go a long way toward solving some of the aboveproblems for some types of fabrics, many deficiencies have remained. Theproblems have been particularly acute in regard to the coloring of glassfibers and synthetic textile fibers, especially those which arerelatively hydrophobic and which are thus resistant to swelling in theaqueous dyebaths normally employed. Dyestufis have been forced into thelatter types of fibers by the use of chemical swelling agents orcarriers, or by the use of high temperatures and pressures in the dyeingprocess. These expedients have not furnished satisfactory answers to theproblems, however. Chemical agents have been expensive and are oftentoxic, difficult to remove, or damage the fiber in either theirapplication or removal. High temperature dyeing generally requires veryexpensive equipment in order to operate above atmospheric pressure.

The process of the present invention provides improved dyed textileproducts and can be carried out with a minimum of the diflicultiesdiscussed above. The invention can be particularly described as aprocess for coloring textile fibers which comprises contacting saidfibers with (I) an aqueous dispersion of an organosiloxane copolymerselected from the group consisting of (A) water miscible copolymersconssiting essentially of polymeric units 3 ,5 l 2 ,9 l 5 Patented May19, 1970 "ice (1) of the formula R," z.,1 u)siY,0

where R is an aliphatic hydrocarbon radical containing a number ofcarbon atoms selected from the group consisting of 1 and more than 2carbon atoms and having a valence of n+1 where n is an integer of atleast 1, Z is a monovalent radical attached to R by a carbon-nitrogenbond and is composed of carbon, nitrogen and hydrogen atoms and containsat least 2 amine 1 groups, the ratio of carbon atoms to nitrogen atomsin g the substituent --RZ being less than 6:1, each R" is a monovalenthydrocarbon radical free of aliphatic unsaturation, Y is selected fromthe group consisting of (OH) and (OR) radicals where R is an alkylradical of less than 4 carbon atoms, x is an integer of from 0 to 2inclusive, z is an integer of from 0 to 2 inclusive, and the sum of x+zhas a value of from 0 to 2 inclusive, and polymeric units.

(2) of the formula II R, 's1Y...o

where each R' is selected from the group consisting of monovalenthydrocarbon radicals and halogenated aryl radicals, Y is as abovedefined, y is an integer of from 0 to 3 inclusive, m is an integer offrom 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3inclusive, there being at least 5 percent by weight of the (1) unitspresent in the copolymer and the copolymer having an average degree ofsubstitution of at least 1 organic group attached directly to silicon bycarbon-silicon bonding per silicon atom and said copolymer having anamine nitrogen content of at least 0.5 percent by weight, and

(B) Water dispersible acid salts of (A), and (II) a textile dyestuff.

The described process is applicable to all textile fibers, both naturaland synthetic. Natural cellulosic fibers such as cotton, linen, andwood, as well as natural protein fibers such as wool and silk, presentfewer dyeing problems than do the synthetics, however, and thusgenerally will not be as greatly benefited as the latter. Nevertheless,cellulosic fibers do not take well to acid dyes because they containonly OH groups as dye sites, and treatment with the definedorganosilicon compounds does permit the use of acid dyes on such fibers,thus leading to greater versatility in dyeing processes.

The greatest benefits from the practice of the present invention arederived in the coloring of glass fibers and the hydrophobic syntheticorganic textile fibers. The term hydrophobic is not necessarily usedhere in the limited sense that some special chemical treatment has beengiven to the fibers to render them unusually water repellant, althoughthe invention is of great benefit in any such case. The term is usedhere in a broader sense with reference to those fibers which have arelatively greater negative surface potential when immersed in distilledwater than do the pure natural cellulosic fibers [see J. Soc. DyersColourists, 71, 102 (1955)], and/or which have very small interstitialcanals, either of which results in little or no swelling in aqueousmedia.

Typical examples of hydrophobic synthetic fibers include such well knownfibers as glass, acrylic (at least 85 acrylonitrile units), modacrylic(at least 35% but less than 85% acrylonitrile units), polyester (atleast 85% an ester of a dihydric alcohol and terephthalic acid), acetate(cellulose acetate and triacetate), Saran (at least vinylidene chlorideunits), nytril (at least long chain polymer or vinylidene dinitrile),nylon (long chain polyamide with recurring amide groups in the chain),Vinyon (at least 85% vinyl chloride units), and olefin (at least 85%ethylene, propylene, or other olefin unit). The generic names anddefinitions of these fibers have been adopted by the Federal TradeCommission under the authority of the Textile Fiber ProductsIdentification Act approved Sept. 2, 1958, and are abstracted in TextileWorld, vol. 109, No. 7, at page 44 (July 1959). Examples of these wellknown types of fibers are commercially available under such names asOrlon, Zefran, Acrilan, Dacron (Terylene), Darvan, Dynel, and Arnel, aswell as under the generic names themselves in many instances, as forexample nylon 6 or 66, and Saran.

Some of the above synthetic polymers are also available in the form offilms or sheets as well as in the form of fibers. Mylar, for example, isessentially Dacron in a film form. Obviously the process of thisinvention is applicable to the dyeing of such films. It will also beobvious that the invention is applicable to the above fibers regardlessof any mechanical processing to which they may have been subjected,i.e., the twisted, crimped, or stretched forms of yarns and the knitted,woven, plaited, braided, or felt fabrics can be treated in that form.

Other hydrophobic textiles to which the invention is applicable includethe metallic yarns such as lam, Lurex, and Metlon, and the variouscombinations of metallic and organic fibers or yarns. The metallic yarnscan be of metal, plastic-coated metal, or metal-coated plastic. Anymetal used in the commercial metallic yarns is suitable here, butaluminum is preferred.

Any textile dyestufi can be used in the present invention. The termdyestufi is used herein to include all textile coloring agents, i.e.both the true dyes and those coloring agents classified separately bysome authorities as pigments or lakes. Dyestuffs are conventionallyclassified by several different systems, for example according to color,origin (e.g. natural, such as madder and indigo, or synthetic, coal tar,etc.), chemical class (azo, anthraquinone, triphenylmethane, etc.),method of application or dyers class (acid, basic, direct, mordant, vat,and developing dyes and lakes and pigments), and on the basis of themost important fibers on which they have been used (e.g. acetate dyes).Obviously there is considerable overlapping between various classeswithin one system as well as between systems, but members of any ofthese classes can be used.

The following are illustrative of the chemical classes of dyes which areused, as classified by the Society of Dyers and Colourists: nitroso,nitro, mono-, di-, tris-, and tetrakisazo, stilbene, pyrazolone,ketimine, diand triphenylmethane, xanthene, acridine, quinoline,thiazole, indamine, indophenol, azine, aniline black, oxazine, thiazine,sulphide, hydroxyketone, hydroxylactone, anthraquinone (acid, vat, andmordant), arylidoquinone, and indigoid. The important chromophores(color bearers) in the above dyestufis are the azo(N=N-), thio (C=S),nitroso(N=O) and groups, along with the weaker nitro(NO carbonyl(C=O),and ethenyl(C=C-) groups. The auxochromes (which affect the intensity ofthe color) in the important dyes are the N(CH3)z NHCH NH OH, and OCHgroups.

Acid dyes are one of the most important and useful dyes in thisinvention. They usually contain or are derived from dyes containingsulfonic acid (SO H) groups, and are generally marketed in the form ofthe water soluble salts containing SO Na groups. They are applied fromdyebaths having a pH ranging from 2 to 8, which may be obtained byadjusting the bath with acids such as sulfuric, formic, or acetic orwith salts such as ammonium sulfate. C.I. Acid Red 5 (14905) is a goodexample of an acid dye.

Many metallizable dyes (eg. chrome dyes, mordant dyes) are acid dyes.This latter type of acid dye has an organic structure such that complexcompounds can form with metals such as chromium to produce awater-insoluble product. The metal can be added before the dyest-uff(bottom-chrome method), with the dyestuff (metachrome or chromateprocess) or after the dyestuif (top, or afterchrome process). C.I.Mordant Yellow 1 14025), C.I. Mordant Red 9 (16105), and Cl. Mordant'Brown 12 are examples of dyes which can be used in any one of the abovethree methods. (Cl. stands for the Color Index classification of theAATCC and the Society of Dyers and Colourists of Bradford, England.) Thefive digit number appearing in parentheses behind the names of thedyestuflfs is the color index number as found in the Technical Manual ofthe American Association of Textile Chemists and Colorists and publishedby the American Association of Textile Chemists and Colorists. Chromium(as sodium bichromate) is the most widely used mordant, but other metalsalts such as copper sulfate, aluminum sulfate, iron sulfate, and tinchloride can be used in similar fashion.

Acid dyes are also available in the form of pre-metallized acid dyes inwhich the metal is already complexed with the organic dye molecule, asfor example in C.'I. Acid Yellow 98, Cl. Acid Green 35 (13361), and Cl.Acid Blue 158 (14880). Many of such dyes are water soluble. Those inwhich one atom of metal has combined with one dye molecule are known as1:1 complexes, and are applied from an acid bath. Neutral dyeing typesare also available as 2:1 dye to metal complexes.

Direct or substantive dyes also are of use in this invention. These dyesusually contain the sodium sulfonate group as the solubilizing group andare characterized by long molecular structures in which the aromaticrings are capable of assuming a coplanar configuration. The benzidinebased dyes are illustrative of this type.

Most of the direct dyes can also be classified as azo dyes, as can manyof the acid and disperse dyes. Azo dyes are prepared by diazotization ofa primary aromatic amine by nitrous acid, followed by coupling theresulting diazonium salt with aromatic amino or hydroxy compounds suchas Naphthol AS. Azo dyestuffs can contain the solubilizing SO Na groups,or can be insoluble pigments. When an insoluble azo dyestuif is formedright in the fiber it is known as an azoic dye. In this latter instance,the dyer can impregnate the fibers first with the aforementionedcoupling compound and then with the diazonium salt, so that couplingtakes place within the fibers. When the primary aromatic amines used fordiazotization in the preparation of azo dyes are applied to textilefibers and diazotized right on the fiber, and the product then coupledas above, the dye is known as a developed dye or color. Any of these azoor azoic dyeing techniques can be used in this invention.

The disperse or acetate dyes are generally small molecules containingamino groups and are only slightly soluble in water, hence they aredispersed rather than dissolved in neutral or slightly alkaline bathsfor application to fibers. Dispersing agents such as soap are used toprevent agglomeration of dyestuff particles in the bath. Although thedisperse dyes were originally of most importance in the dyeing ofacetate fibers, they are now used with almost any of the man-made fibersand can be used 1n this invention. These dyes belong to various chemicalgroups, anthraquinone, aminoazo, pyrazolon, and indophenol types beingillustrative. Typical examples of specific dyes of this type are C.I.Disperse Violet 4 (61105), C.I. Disperse Yellow 14, and Cl. DisperseOrange 3 (11005).

Vat dyes also are of interest here. For the most part they are insolublecompounds and are usually anthraquinone, or thioindigoid derivatives.They are characterized by the presence of 0 0 groups which can bereduced with an agent such as sodium hydrosulfite to COH groups. Thereduced form is known as the leuco form, and is soluble in caustic sodasolutions, forming C--ONa groups. After application to textiles, thelatter are oxidized to their original form by exposure to air or toagents such as sodium perborate, hydrogen peroxide, etc., and the dyeingprocess is usually then completed by exposing the textile fibers to hotsoap or detergent solutions. Soluble vat dyes are also available. Theseare generally in the form of salts of the sulfuric acid esters of theleuco form of the dye, i.e. they contain C--OSO Na groups.

The sulfur dyes are mixtures of complex sulfur-containing organiccompounds, and are further examples of dyes which can be used herein.Like vat dyes, the sulfur dyes must be reduced in an alkaline medium forapplication. Na S is generally both the reducing agent and the source ofalkali to bring about the solution of the reduced form.

The so-called chemically reactive dyes are also of use here. Such dyesordinarily contain solubilizing groups, an organic molecule portionfurnishing the chromophores, and sustituents such as halogen,particularly chlorine, which are capable of reacting directly withcellulosic OH groups. As used herein, such dyes can react not only withany OH groups present in the textile fiber being treated, but also mayreact with functional groups in the organosilicon compound employed.

The basic dyes are another large class of dyes which can be used in thisinvention, although they are usually less desirable than other types.These are dyes in which the so-called colored portion of the dyemolecule carries a positive charge when the dye is in solution. Thesedyes are generally marketed in the form of chloride or sulfate salts ofthe basic organic molecule which makes up the colored portion of thedye. Typical salts are those containing the NH Cl group, as in CI. BasicOrange 2 (11270). Because basic dyes exhaust rapidly from a dyebath,they are usually used in conjunction with a retarding agent. On somefibers, particularly vegetable fibers such as cotton, the basic dyes aregenerally applied after the fiber has been first mordanted with an acidmaterial such as tannic acid.

As has been noted previously, the term dyestuff is used herein toinclude pigments as well as dyes. Textile pigments are well knownmaterials, and any such. can be used here. The term resin bondedpigments covers the class of pigments which is most useful herein. Thelatter are often referred to by an RB number, which is a designationassigned by the American Association of Textile Chemists and Colorists.Typical pigments include those of carbon black, dianisidine blue,phthalocyanine blue or green, Ultramarine blue, iron oxide brown or red,metallized azo brown, benzidine orange or yellow, chrome orange oryellow, titania, zinc oxide, indomaroon, and lithosol yellow. Blends ofdifferent pigments are often made to achieve a particular color.Pigments are often marketed in the form of neutral or alkaline aqueousdispersions.

It is to be understood that when reference is made herein to contactingthe fibers with a textile dyestufi, the dyestuff can be a single entityor a multiple entity and can be applied by a single step or a multiplestep process. In other words, the conventional applications such asthose discussed above are contemplated here, and applying a dyestuif caninclude such diverse processes as those in which two or more colorlessmaterials are applied separately or in which mordants, soaps, detergentsor other materials which are not dyestuffs themselves are conventionallyapplied as a part of the dyeing process. Some dyestuffs can be appliedfrom solutions in organic solvents, but water dispersible dyestuffs arepreferred in the industry and in this invention. The term waterdispersible is used to include materials which are truly water solubleas well as those which are insoluble or only very slightly soluble inwater and hence which are applied as suspensions of finely dividedparticles in water, usually in the presence of a surface active agent toassure good dispersion of the particles. In general, the water solubledyestuffs are preferred.

The organosiloxane copolymers employed in this invention consistessentially of polyaminoalkyl substituted siloxane units of the formulaand conventional siloxane units of the formula with there being at least5 percent by weight of the former units present. In these formulae, xand z are integers of from 0 to 2 inclusive and the sum of x+z has avalue of from 0 to 2 inclusive, y is an integer of from 0 to 3inclusive, m is an integer of from 0 to 2 inclusive, and the sum of y+mhas a value of from 1 to 3 inclusive. The average values for any ofthese subscripts can be fractional when the copolymer as a whole isconsidered. The amounts of the two types of polymeric units present inthe copolymer and the values of x and y in each unit should be such thatthere is an average of at least one organic group attached directly tosilicon by carbonsilicon bonding per silicon atom. In other words, theratio of R+R"'+(Z R) groups to Si atoms is at least 1:1, i.e., theaverage degree of substitution is at least 1. It will be seen that theaverage degree of substitution can be as high as 3, but preferably itranges from 1 to about 2.05 inclusive. The amine nitrogen content of thecopolymer should be at least 0.5 percent by weight. It is most preferredthat x be 0 or 1, y be 2, and z be 0 or 1, and that there be at least 15percent by weight of the polyaminoalkyl substituted siloxane unitspresent.

In the defined polymeric units, R can be any aliphatic hydrocarbonradical containing 1 or more than 2 carbon atoms and having a valence ofat least two, i.e. it can include, in any aliphatic configuration, anycombination and any number of methyl, vinyl, methylene, vinylene,

groups within the scope of the claims.

Each Z can be any monovalent radical attached to R through acarbon-nitrogen linkage, which is composed of hydrogen, carbon andnitrogen atoms, in which preferably all of the nitrogen atoms arepresent as amine or nitrile groups, and in which there are at least twoamine groups per Z radical. The term amine groups comprises primaryamine, secondary amine (including imine) and tertiary amine groups. Thescope of Z will be better understood from a consideration of the methodof producing these siloxanes.

R can be any monovalent hydrocarbon radical free of aliphaticunsaturation. Preferably, however, it contains a maximum of 18 carbonatoms. Illustrative examples of suitable R" radicals include alkylradicals such as methyl, ethyl, propyl, isopropyl, butyl and octadecyl;aryl radicals such as phenyl, xenyl, and naphthyl; alkaryl radicals suchas tolyl and xylyl; aralkyl radicals such as benzyl; and cycloaliphatieradicals such as cyclohexyl. Methyl, ethyl, and phenyl are mostpreferred.

The Y radicals in the above formulae represent (OH) and/or (OR) radicalswhere R represents an alkyl radi cal of less than 4 carbon atoms, i.e.,methyl, ethyl, propyl, or isopropyl radicals.

In the conventional siloxane units each R can be any monovalenthydrocarbon radical or halogenated aryl radical. Examples of suitableradicals include all of the illustrative R radicals listed above, aswell as alkenyl and alkynyl radicals such as vinyl, allyl, cyclohexenyl,and propynyl; and halogenated aryl radicals such as bromophenyl,dichlorophenyl, chloroxenyl, a,a,ot-lllfiu0l0- tolyl, and the like.

In the defined units, each R, R, R, R, Z, or Y radical can of course bethe same as or different from each of its fellow radicals in thecopolymer.

The preferred method for the preparation of the defined copolymers isthat which is illustrated in detail in the copending application ofLawrence H. Brown, filed concurrently herewith and entitled Method forthe Preparation of Aminoalkylsiloxane Copolymers. In brief, this methodcomprises mixing the appropriate amounts of a(polyaminoalkyl)alkoxysilane, i.e.

with a conventional organosiloxane containing a substantial amount ofsilicon-bonded hydroxy groups, for example, 1 to percent by weight OH.The former reacts with the latter to form new siloxane bonds, asillustrated by the simplified equation:

ESlOR+HOSiE ESlOSlE +ROH The reaction is preferably speeded up byheating the mixture, as for example at 100 to 200 C. Inert solvents canbe present if desired. The alcohol which is formed in this reaction canbe removed by disillation, thus it is certain that true copolymers areformed. It will be readily apparent that the copolymer can haveunreacted (OR) and/or (OH) groups present, depending upon the relativeamounts of the two reactants and the amount of (OR) or (OH) present inthe reactants initially. If de sired, excess (OR) groups can behydrolyzed by the addition of Water to the system, and controlling theamount of water so added controls the amount of such groups which remainin the copolymer. Likewise, excess (OH) groups can be caused tocondense, as for example by heating the copolymer. Any or all of thealcohol formed by either the initial reaction or any subsequenthydrolysis can be left in the reaction product, if desired. In aqueoussolutions or dispersions, the copolymer actually is in a state ofequilibrium, and determination of the precise amounts of silicon-bonded(OH) or (OR) present is ordinarily not feasible.

Another method for the preparation of the copolymers employed in thisinvention is by the cohydrolysis of the (polyaminoalkyl)alkoxysilanesreferred to above with the conventional alkoxysilanes of the formula R'Si(OR) The preparation of such cohydrolyzates can be by conventionaltechniques, and is set forth in detail in my aforesaid copendingapplication Nos. 753,115 and 753,153.

The (polyaminoalkyl) alkoxysilanes employed to prepare the copolymersused herein can be produced by the techniques set forth in greaterdetail in the above mentioned copending applications and in my aforesaidcopending application Ser. No. 723,991. Thus they can be produced byreacting a polyamine with a halogenohydrocarbonalkoxysilane where eachhalogen atom is on a car- 'bon atom at least gamma to the silicon atom.Alternatively, they can be prepared by reacting the polyamine with analpha-halogenohydrocarbonalkoxysilane. In these reactions one nitrogenin the polyamine replaces a halogen atom in the halogenohydrocarbonradical, and the halogen acid is given off. The reaction is best carriedout at temperatures of from 50 to 200 C. under anhydrous conditionsusing a molar excess of the polyamine.

The polyamines which can be employed include, for example, thefollowing: ethylenediamine, diethylenetriamine, 1,6 hexanediamine, 3aminoethyl--l,6-'diaminohexane, N,N dimethylhexamethylenediamine,cadaverine, piperazine, dl-1,2-propanediamine, methylhydrazine, 1aminoguanidine, 2 pyrazoline, benzenetriamine, ben- Zenepentamine,benzylhydrazine, N-methyl-p-phenylenediamine, N,N dimethyl pphenylenediamine, and 3-0- tolylenediamine.

It can be readily seen that the polyamine employed can be any aliphatic,cycloaliphatic or aromatic hydrocarbon amine containing at least twoamine groups, one of which must contain at least one hydrogen atom. Theterm poly in the specification is intended to include compounds orradicals containing two or more amine groups.

The halogenohydrocarbonsilanes employed in the above described processcan themselves be prepared by the well known addition reaction of ahalogenated aliphatic hydrocarbon containing at least one unsaturatedcarbon to carbon linkage, with a halosilane such as that of the formulaR" SiHCl where R" and x are as previously defined, after Which theaddition product is alkoxylated by reacting it with one or more alcoholsof the formula ROH. Examples of suitable halogenated hydrocarbonsinclude allylbromide, allyliodide, methallylchloride, propargylchloride,l chloro- 2 -methylbutene-2, 5- bromo pentadiene 1,3, 16 bromo2,6dimethylhexadecene-2, and the like. The halogenohydrocarbons cancontain more than one halogen atom, as in 3,4-dibromobutene-l and3-chloro-2-chloromethylpropene-l, so that the radicals resultingtherefrom can react with more than one amino nitrogen atom, i.e. n canbe greater than 1. Preferably there should be no more than one halogenatom per carbon atom. Furthermore, no halogen atom can be so positionedthat after the addition of the halogenohydrocarbon to the silicon thereis a halogen atom on a carbon atom which is beta to the silicon.

A second method for preparing the halogenohydrocarbonsilanes describedabove is that of halogenating an alkylhalosilane with elemental halogenfollowed by reaction with an alcohol to give thehalohydrocarbonylalkoxysilane. This is the method employed when R in theabove formula is a methylene radical.

The radical (RZ can be of any length, so long as the ratio of carbon tonitrogen in the radical is less than 6:1. As a practical matter, the Rradicals will ordinarily contain no more than 18 carbon atoms, andpreferably contain 1 or 3 to 5 inclusive carbon atoms. The preferred Zradicals contain from 1 to 8 carbon atoms, and n is preferably 1, 2, or3.

The acid salts which can be employed herein can be prepared bycontacting the defined copolymers in a liquid phase with the chosenacid. The acid can be organic or inorganic, and is preferably a watersoluble acid such as hydrochloric, hydrobromic, nitric, acetic, formic,propanoic, and lactic acids. The salts are generally used in situationswhere the alkalinity of the amine groups is undesirable, or where agreater degree of water solubility is desired in the organosiliconcompound. In preparing the salts, ordinarily the acid will be used in anamount to provide about one equivalent of acid for each amine nitrogenatom present in the copolymer. Of course any amount less than this canbe used, if desired, to provide a partial salt having solubilitycharacteristics intermediate between the copolymer per se and the fullsalt. Such a partial salt is meant to be included within the scope ofthe term acid salt as it is employed herein. An excess of acid over theequivalent amount can also be used, subject only to the practicallimitation imposed by any harm which a large excess of acid might do totextiles or dyestufis in contact with a system which is too highly acid.

The defined copolymers or salts used in the process of this inventionare water-miscible materials. The term water miscible is used herein asinclusive of both water soluble and self-emulsifiable materials. Ingeneral, the the salts defined herein are truly water soluble in theusual sense of that term. The same is also true of those copolymerswhich are not salts but which contain a sufficient amount of thepolyaminoalkyl substituted polymeric units to impart water solubility.In a dimethylsiloxane copolymer system, for example, those copolymerswhich contain at least 20 to 25 percent by weight of the polyaminoalkylsubstituted units will generally be truly Water soluble. Copolymerscontaining a. lesser amount of polyaminoalkyl substituted units, e.g. 5to 20 percent in the aforesaid di methylsiloxane copolymer system, aregenerally selfemulsifiable. By this it is meant that the lattercopolymers donot form true solutions, but do form stable emulsions 9with water, even in the absence of any added emulsifying agent, i.e., nothird ingredient is necessary to form an emulsion.

The organosilicon compounds defined herein can have a beneficial resultin the dyeing process regardless of at what stage in the process theyare applied to the textile fibers. For example, the fibers can bepretreated prior to coloring by contacting them with the organosiliconcompound. Preferably the fibers are then dried before proceeding withthe coloring step, but this is not necessary in some cases. If used, thedrying step can be carried out at room temperature but preferably isexpedited by heating the treated fibers at temperatures of, for example,from 125 to 400 F. (i.e., about 52 to 204 C.). Such heat treatments alsotend to improve the fastness of the final colored product.

The pretreatment technique is in general the most preferred one. Goodresults can also be obtained, however, by mixing the organosiliconcompound, water, and textile dyestutf, then applying the entire mixtureto the fibers. The application step is then followed by drying thefibers and by any additional steps required for the particular dyestutfemployed. When a mixture is used in this fashion, it can be appliedeither to the bare textile fibers or to fibers which have beenpretreated with the organosilicon compound as described above.

A third alternative technique is to first color the fibers by any of theconventional processes, and then treat the colored product with theorganosilicon compound.

In any of the application techniques discussed above, conventionalprocesses (such as padding, spraying, or immersion in a treating bath toexhaust the treating material onto a textile) can be used to apply thedyestuff and/or the organosilicon compound. The textile fibers orfilaments can be treated as such, or in the form of threads, yarns,fabrics, finished garments, etc. If desired, the treated and coloredproducts obtained by practicing this invention can be further treatedwith other compounds to render them Water repellent or wrinkleresistant, or to provide a softer hand in the finished fabrics, etc.Aftertreatments with organosilicon compounds such as those described inUS. Pats. 2,807,601; 2,728,692; 2,588,365; and 2,588,366 are often mostdesirable. The present invention can also be useful in coloring textileswhich have been pretreated in accordance with the aforesaid U.S.patents.

Aqueous solutions or emulsions of the defined copolymers or copolymersalts can be applied to the textile fibers at any desired concentration.Ordinarily the best results will be obtained by employing materialhaving a concentration of the defined organosilicon compounds rangingfrom about 0.1 to 5.0 percent by weight, preferably from 0.3 to 2.0percent. This concentration will generally provide the 0.2 to 0.8percent by weight pickup of organosilicon compound which is preferredfor most fibers. It is often desirable to incorporate a water-misciblesolvent (such as the lower aliphatic alcohols dioxane, tetrahydrofuran,etc.) into the aqueous systems employed herein, as an aid in speedingthe attainment of homogeneous solutions or emulsions.

Copolymer preparation In the following description and examples, thesymbols Me, Et, Vi, and Ph have been used to represent methyl, ethyl,vinyl, and phenyl radicals respectively. Copolymers and salts for use inthe examples were prepared by the following general technique, whichspecifically illustrates the preparation of a 75/25 copolymer:

A mixture was prepared containing 75 g. (MeO Si CH NHCH CH NH and 25 g.of a polymer having the formula (HO Me SiO (Me SiO SiMe (OH) where theaverage value of a was such that the polymer contained 3.5 percent byweight of (OH) groups. Such a mixture contains about 1.01 mols (OMe)groups and 0.05 mol (OH) groups. The mixture was heated to 150 C. undera refiux condenser, then 8.65 g. H O (0.48 mol, equivalent to the 0.96molar difference between the OMe and OH groups) was added, followed by75 g. EtOH (sufficient to provide a solution of about 50 percent of thetheoretical organosiloxane product). About one third of the alcohol wasremoved by distillation and then the product was readjusted to a 50percent concentration. The resulting ethanol solution is completelysoluble in water, and the copolymer product present therein containedabout 75 percent units and 25 percent Me SiO units, by weight. The valueof z in this copolymeric solution could not be measured because of thealcohol present as solvent, but theoretically would range between 0and 1. When the alcoholic solution of such a copolymer is itselfdissolved in water, a major portion of any residual silicon-bondedmethoxy groups are hydrolyzed. When such an aqueous solution is appliedto a textile and the treated material is dried, hydrolysis andcondensation of the copolymer become substantially complete so that thecopolymer consists essentially of only Me SiO and units.

A salt of the copolymer described above was prepared by adding 40.5 g.acetic acid (0.676 mol) to the cool 50 percent alcohol solution, thusproviding 1 mol of acid for each gram atom of nitrogen present in thecopolymer.

Copolymers and salts similar to those specifically illustrated abovewere made from the same reactants by the same technique, but usingratios of 10/90, 25/75, 50/50, and /10 in place of the 75/75 ratiodescribed above. Related 50/50 copolymers were prepared by the sametechnique, except that (M60 MeSi (CH NHCH CH NH (MeO or (MeO) Si(CH NHCHCH N(CH CH CN) were used in place of the (MeO) Si(CH NHCH CH Nl-Ireactant.

In the following examples, all parts and percentages are by weightunless otherwise indicated.

EXAMPLE 1 A series of aqueous solutions was prepared by mix ing 98 partsof Water with 2 parts respectively of each one of the 50 percent alcoholsolutions of the various copolymers and salts described above underCopolymer Preparation. Thus aqueous solutions were obtained whichcontained 1 percent respectively of the 10/90, 25/75, 50/50, 75/25, or90/ 10 copolymers (where the designation 10/90 etc. refers to thetheoretical ratio of units to Me SiO units) or 1 percent of therespective 50/50 copolymers specifically described above, where thepolyaminoalkyl substituted units were NHgCHgCHgNH (CH SiMeO or units,01' 1 percent of the respective acetate salts of these variouscopolymers. All of the salts, and all of the copolymers except the10/90, formed true aqueous solution. The 10/ 90 copolymer formed astable emulsion.

A number of test pieces of undyed Orlon, Dacron, nylon, acetate, cotton,silk, wool, viscose, and glass fiber textiles were each padded with oneof the solutions by dipping into the solution and running the wet fabricthrough squeeze rollers. The pickup of organosilicon compound was about0.5 percent in each case, based on the weight of the fabric. The Orlonsamples were dried for 5 minutes at 260 F., and all others were driedfor 20 minutes at 255 F. Specimens of each treated fabric were then dyedwith various dyes as shown below.

Part A A number of acid and metallized acid dyes were applied to thetreated fabrics by the following exhaustion technique. Aqueous solutionsof each dye were made up containing 3 parts dye, 2 parts ammoniumacetate, and 100 parts water based on the weight of the test fabric.Each specimen of fabric was immersed in one of the solutions for 30minutes while the solution was held at 170 F., and was then rinsed withcold water and allowed to dry at room temperature. The dyes employedwere as follows, with Color Index designations being shown inparentheses: Cibalan Black BLG, Erio Fast Brown 5 GL, Supranol Orange RA(C.I. Acid Orange 45) (22195), Pontacyl Green BL (Acid Green 3) (42085),Nigrosine ESB Extra (C.I. Acid Black 2) (5042 Calcocid Fast Light Orange2G (C.I. Acid Orange 10) (16230), Erio Anthracene Blue 4 GL (C.L. AcidBlue 23) (61125), Gycolan Dark Green BL (C.L. Acid Green 35) (13361),Kiton Fast Orange GR (C.I. Acid Orange 22), Brilliant Croceine 3 BA(C.I. Acid Red 73) (27290), Kiton Red S (C.I. Acid Red 7) (14895),Cibalan Yellow GL (C.I. Acid Yellow 114), Cibalan Orange RLW (C.I. AcidOrange 86), Cibalan Brown 2 'RL (C.I. Acid Brown 45 Cibalan Bordeaux GRL(C.I. Acid Red 213), Calcofast Brown MF (C.I. Acid Brown 97), andCalcofast Olive Brown G (C.I. Acid Brown 93). Treated fabrics were alsodyed with Neolan Yellow BE (19010), using the same technique except that4 parts H 80 were used in place of the salt in the dye solution.

Each of the above treated fabrics had a good depth of shade and a goodcolor yield from. each of the dyes. Orlon, cotton, glass and Dacronfabrics which had no pretreatment were only poorly dyed or not coloredat all when subjected to the same dyeing process, i.e., they were atbest only slightly stained by the dyes.

Part B Direct dyes were applied to the treated fabrics by padding withsolutions containing 0.55 part dye, 100 parts water, and 0.5 partTergitol TMN (a trimethylnonyl ether of polyethylene glycol used as awetting agent). The dyed fabrics were then heated for 5 minutes at 260F., rinsed with cold water, and dried at room temperature. The dyesemployed were Chlorantine Fast Orange GRLL (C.I. Direct Orange 34)(40215/20-,) Chlorantine Fast Red 5 BRL (C.I. Direct Red 80) (35780),Chlorantine Fast Blue 2 RLL (C.I. Direct Blue 80), and Calcomine SkyBlue FF Extra Conc. (C.I. Direct Blue 1) (24410). Each fabric had a gooddepth of shade and color yield, whereas Orlon, Dacron, glass and woolfabrics were only slightly stained when these dyes were applied withoutthe organosilicon pretreatment.

Part C Solutions containing 0.55 part of a reactive dye, 100 partswater, and 0.5 part Tergitol TMN were padded onto the organos'ilicontreated fabrics, and the wet fabrics were dried for 5 minutes at 260 F.The dried fabrics were then washed in soapy water at 56 C., rinsed withcold water, and dried at room temperature. The dyes employed were theCibacron dyes Turquoise Blue G, Yellow R, Black BG, and Brilliant Red 3B; the Remazol dyes Yellow G and Red B; and the Procion dyes BrilliantBlue R, Yellow R, Brilliant Red 5 B and 2 B, Brilliant Yellow 6 G, andPrinting Green 5 G. Each fabric had a good depth of shade and coloryield, whereas again untreated glass,

12 Orlon and Dacron would only take a slight stain from the same dyes.

Part D Disperse dyes Eastone Red B (C.I. Disperse Red 30) and EastoneOrange 3 R (C.I. Disperse Orange 17) were applied to the treated fabricsby the exhaustion technique of Part A above. Each fabric was found to betruly dyed and not merely stained, although the depth of shade obtainedwas less satisfactory than that obtained in Parts A to C above.

EXAMPLE 2 A single bath dyeing process was carried out by preparingsolutions of 2.2 parts of a reactive dye, 2.44 parts of the respective50 percent alcohol solutions of the 50/50 copolymers described inExample 1, and parts of water, padding samples of each untreated fabricof Example 1 with one of the solutions, drying each fabric at roomtemperature followed by 5 minutes heating at 260 F., then washing eachfabric in warm soapy water, rinsing with cold water, and again dryingthe fabric at room temperature. The reactive dyes employed were ProcionBlue 3 G and Procion Red B. All of the fabrics were suitably colored :bythis technique. Greater bath stability was obtained in this system 'byadding NH OH up to a final concentration of 10 percent.

EXAMPLE 3 When (EEO EtSi CH gNHCHgCHgNHg,

(E) 2PhSi CH gNHCHzCHzNHZ (M60 )gSiC Hz C H2 0 HNH C H2 0 HZNHZ,

HQNI'IC HQCIIZNHZ (MeO sicn stnc nns Me (M00 S1 CH NH (CH NHz s 2 a s az 2 or (MeO) Si(CH NMe(CH NHMe is substituted for the (MeO) Si(CH NHCHCH NH used in the preparation of the copolymers shown in Example 1, andthe resulting copolymers and salts are used for fabric treatment anddyeing processes in accordance with that example, comparable results areobtained.

EXAMPLE 4 The various 1 percent solutions in water of the copolymers ofExample 1 were mixed with formic, adipic, hydrochloric, or nitric acidsrespectively in an amount to provide 1 molecule of the acid for each Natom, thus forming the respective salts. When these salt solutions areemployed to treat the fabrics of Example 1 by the technique employed inthat example, and the treated fabrics are then dyed as in that example,the dyed fabrics have a comparable depth of shade and color yield.

EXAMPLE 5 The organosilicon-treated fabrics of Example 1 were eachpadded with various commercial pigment dyestuffs in the form of aqueoussuspensions or dispersions containing about 5 parts of the as-marketeddispersion and 95 parts water. After padding, the fabrics were dried atroom temperature and then heated for 5 minutes at 250 F. Each sample hada good depth of shade and color yield. Equivalent results were obtainedfrom a single bath system by padding the untreated fabrics with asolution of 1.0 part of one of the organosilicon copolymers of Example 1and 94.0 parts water in which there was dispersed 5 parts of any one ofthe as-marketed dispersions of the same commercial pigments, followed byair drying the fabrics and heating them for 5 minutes at 250 F Thecommercial pigment dispersions employed in both of the above dyeingprocesses were the alkaline dispersion types Aridye Gray K (RB 10),Aridye Yellow N (RB 93), Aridye Yellow K (A.A.T.C.C. designation 13 RB92) Aridye Brown R (RB 31), and Primal Burgundy; and the Aridye SXNneutral dispersion compositions Brown R (RB 31), Red B (RB 60), Yellow R(RB 94), Blue 2 G (RB 20), and Green B (RB 40). These commercial pigmentdispersions contain from about 25 percent to about 60 percent solids,and the extent to which they are diluted for application to fabricsdepends almost entirely upon the shade of color desired on a particularfabric.

EXAMPLE 6 When paper or any fabrics of the acrylic, modacrylic,polyester, Saran, nytril, or polyethylene types are pretreated as inExample 1 and dyed as in Parts A to D of that example, the materialspickup good deep shades of the color employed. The shade obtained fromany particular dye could be varied over a wide range by varying theconcentration of dye in the dyeing bath.

EXAMPLE 7 A series of copolymers was prepared by mixing the amine (MeO)Si(CH NHCH CH NH with one or more of various conventional alkoxysilanes,heating the mixture to 50 to 100 C., and slowly adding water up to anamount equivalent to the alkoxy groups present. The entire reactionproduct from each was diluted with water to a concentration of 1 percentorganosiloxane content and each solution was neutralized with 1 molacetic acid per gram atom of nitrogen. The types and weight ratios ofsilanes employed were as follows:

(A) 25 amine/75 Me Si(OEt) (B) 50 amine/25 Me Si(OEt) /25 MeSi(OEt) (C)54 amine/46 ViSi(OEt) (D) 50 amine/25 MePhSi(OEt) /25 C1 C H Si(OEt) (E)70 amine/30 PhSi(OEt) (F) 70 amine/10 Me Si(OEt) /1O MeSi(OEt) /1O MeSiOEt When the 1 percent solutions of the salts of the abovecohydrolyzates are used as the organosilicon treatment in the processesof Example 1, approximately the same results are obtained in the dyeingoperations of that example.

The preparation of the various (polyaminoalkyD- alkoxysilanes used tomake the copolymers described in the preceding examples is set forth indetail in the copending applications previously mentioned. The compoundcan be prepared by reacting 3 moles of acrylonitrile with 1 mol (MeO)Si(CH NHCH CH NH keeping the exothermic reaction down to about 55 C.until it subsides, heating the reaction product at about 95 C. for 4hours, and flash distilling that mass to a pot temperature of 168 C. at15 mm. Hg pressure to remove the 1 mol of unreacted acrylonitrile. Theresulting residue consists essentially of the desired product, n 1.4615,and is a brown oily liquid.

That which is claimed is: 1. A process for coloring textile fibers whichcomprises contacting said fibers with (I) an aqueous dispersion of anorganosiloxane copolymer selected from the group consisting of (A)water-miscible copolymers consisting essentially of polymeric units (1)of the formula Rn(ZnR')slY;O3 x

Where. R is an aliphatic hydrocarbon radical selected from the groupconsisting of aliphatic hydrocarbon radicals containing 1, 3, 4, and 5carbon atoms and having a valence of n+1 where n is an integer of from 1to 3 inclusive, Z is a monovalent radical attached to R by acarbon-nitrogen bond and which contains up to 8 carbon atoms and iscomposed of carbon, nitrogen and hydrogen atoms and contains at least 2amine groups, the ratio of carbon atoms to nitrogen atoms in thesubstituent ---R'Z being less than 6:1, each R" is a monovalenthydrocarbon radical free of aliphatic unsaturation, Y is selected fromthe group consisting of (OH) and (OR) radicals where R is an alkylradical of less than 4 carbon atoms, x is an integer of from 0 to 2inclusive, z is an integer of from 0 to 2 inclusive, and the sum of x+zhas a value of from 0 to 2 inclusive, and polymeric units (2) of theformula R SiYmO where each R'" is selected from the group consisting ofmonovalent hydrocarbon radicals and halogenated aryl radicals, Y is asabove defined, y is an integer of from 0 to 3 inclusive, m is an integerof from 0 to 2 inclusive, and the sum of y+m has a value of from 1 to 3inclusive, there being at least 5 percent by weight of the (1) unitspresent in the copolymer and the copolymer having an average degree ofsubstitution of at least 1 organic group attached directly tosilicon bycarbon-silicon bonding per silicon atom and said copolymer having anamine nitrogen content of at least 0.5 percent by weight, and (B)water-miscible acid salts of (A), and (II) a textile dyestutf.

2. In a process for coloring textile fibers by contacting said fiberswith a textile dyestuff, the improvement which comprises contacting thefibers with an aqueous dispersion of an organosiloxane copolymerselected from the group consisting of (A) water-miscible copolymersconsisting essentially of polymeric units (1) of the formula where R' isan aliphatic hydrocarbon radical selected from the group consisting ofaliphatic hydrocarbon radicals containing 1, 3, 4, and 5 carbon atomsand having a valence of n+1 where n is an integer of from 1 to 3inclusive, Z is a monovalent radical attached to R by a carbon-nitrogenbond and which contains up to 8 carbon atoms and is composed of carbon,nitrogen and hydrogen atoms and contains at least 2 amine groups, theratio of carbon atoms to nitrogen atoms in the substituent ---RZ beingless than 6:1, each R" is a monovalent hydrocarbon radical free ofaliphatic unsaturation, Y is selected from the group consisting of (OH)and (OR) radicals where R is an alkyl radical of less than 4 carbonatoms, x is an integer of from 0 to 2 inclusive, z is an integer of from0 to 2 inclusive, and the sum of x+z has a value of from 0 to 2inclusive, and polymeric units (2) of the formula R ySiYmO 15 therebeing at least 5 percent by weight of the (1) units present in thecopolymer and the copolymer having an average degree of substitution ofat least 1 organic group attached directly to silicon by carbon-siliconbonding per silicon atom and said copolymer having an amine nitrogencontent of at least 0.5 percent by weight, and

(B) water-miscible acid salts of (A).

3. In a process for coloring hydrophobic textile fibers by contactingsaid fibers with a water dispersible textile dyestufi', the improvementwhich comprises pretreating said fibers prior to coloring by contactingthe fibers with an aqueous dispersion of an organosiloxane copolymerselected from the group consisting of (A) water-miscible copolymersconsisting essentially of polymeric units (1) of the formula where R isan aliphatic hydrocarbon radical selected from the group consisting ofaliphatic hydrocarbon radicals containing 1, 3, 4, and 5 carbon atomsand having a valence of ru-l-l where n is an integer of from 1 to 3inclusive, Z is a monovalent radical attached to R by a carbon-nitrogenbond and which contains up to 8 carbon atoms and is composed of carbon,nitrogen and hydrogen atoms and contains at least 2 amine groups, theratio of carbon atoms to nitrogen atoms in the substituent RZ being lessthan 6:1, andeach R" is a monovalent hydrocarbon radical free ofaliphatic unsaturation, Y is selected from the group consisting of (OH)and (OR) radicals where R is an alkyl radical of less than 4 carbonatoms, x is an integer of from to 2 inclusive, 2 is an integer of from 0to 2 inclusive, and the sum of x-i-z has a value of from 0 to 2inclusive, and polymeric units (2) of the formula where each R' isselected from the group consisting of monovalent hydrocarbon radicalsand halogenated aryl radicals, Y is as above defined, y is an integer offrom O to 3 inclusive, m1 is an integer of from 0 to 2 inclusive, andthe sum of y+m has a value of from 1 to 3 inclusive, there being atleast 5 percent by weight of the (1) units present in the copolymer andthe copolymer having an average degree of substitution of at least 1organic group attached directly to silicon by carbon-silicon bonding persilicon atom and said copolymer having an amine nitrogen content of atleast 0.5 percent by weight, and

(B) water-miscible acid salts of (A), and then drying said fibers.

4. A process for coloring hydrophobic textile fibers which comprisescontacting said fibers with a mixture consisting essentially of (I) anaqueous dispersion of an organosiloxane copolymer selected from thegroup consisting of (A) water-miscible copolymers consisting essentiallyof polymeric units (1) of the formula where R is an aliphatichydrocarbon radical selected from the group consisting of 1 and morethan 2 carbon atoms and having a valence of ni+1 where m is an integerof from 1 to 3 inclusive, Z is a monovalent radical attached to R by acarbon-nitrogen bond and which contains up to 8 carbon atoms and iscomposed of carbon, nitrogen and hydrogen atoms and contains at least 2amine groups, the ratio of carbon atoms to nitrogen atoms in thesubstituent -R'Z being less than 6: 1, and each R" is a monovalenthydrocarbon radical free of aliphatic unsaturation, Y is selected fromthe group consisting of (OH) and (OR) radicals where R is an alkylradical of less than 4 carbon atoms, x is an integer of from 0 to 2inclusive, z is an integer of from O to 2 inclusive, and the sum of x+zhas a value of from 0 to 2 inclusive, and polymeric units (2) of theformula R' SiYmO where each R is selected from the group consisting ofmonovalent hydrocarbon radicals and halogenated aryl radicals, Y is asabove defined, y is an integer of from O to 3 inclusive, m is an integerof from O to 2 inclusive, and the sum of y-i-m has a value of from 1 to3 inclusive, there being at least 5 percent by weight of the 1) unitspresent in the copolymer and the copolymer having an average degree ofsubstitution of at least 1 organic group attached directly to silicon bycarbon-silicon bonding per silicon atom and said copolymer having anamine nitrogen content of at least 0.5 percent by weight, and (B)water-miscible acid salts of (A), and

(II) a water dispersible textile dyestuff, and then drying said fibers.

5. In a process for coloring textile fibers selected from the groupconsisting of glass, nylon, polyacrylonitrile, dihydricalcohol-terephthalic acid polyester, polyvinylidene chloride,polyvinylidene dinitrile, cellulose acetate and polyolefin fiber-s witha water dispersible textile dyestuft', the improvement which comprisespretreating said fibers prior to coloring by contacting the fibers withan aqueous solution of a water-soluble acid salt of an organosiloxanecopolymer consisting essentially of polymeric units (I) of the formulawhere Y is selected from the group consisting of (OH) and (OR) radicalswhere R is an alkyl radical of less than 4 carbon atoms, and z is aninteger of from O to 2 inclusive, and polymeric units (II) of theformula (OH )zSi(OH)mO where m is an integer of from 0 to 1 inclusive,there being at least 15 percent 'by weight of the (I) polymeric unitspresent in said copolymer, and then drying said fibers.

6. In a process for coloring textile fibers selected from the groupconsisting of glass, nylon, polyacrylonitrile, dihydricalcohol-terephthalic acid polyester, polyvinylidene chloride,polyvinylidene dinitrile, cellulose acetate and polyolefin fibers with awater dispersible textile dyestuff, the improvement which comprisespretreating said fibers prior to coloring by contacting the fibers withan aqueous solution of a water-soluble acid salt of an organosiloxanecopolymer consisting essentially of polymeric units 1 7 (I) of theformula where Y is selected from the group consisting of (OH) and (OR)radicals Where R is an alkyl radical of less than 4 carbon atoms, and zis an integer of from to 1 inclusive, and polymeric units (II) of theformula where m is an integer of from 0 to 1 inclusive, there being atleast 15 percent by weight of the (I) polymeric units present in saidcopolymer, and then drying said fibers.

7. A process for coloring textile fibers selected from the groupconsisting of glass, nylon, polyacrylonitrile, dihydricalcohol-terephthalic acid polyester, polyvinylidene chloride,polyvinylidene dinitrile, cellulose acetate and polyolefin fibers whichcomprises contacting said fibers with an aqueous dispersion of a mixtureconsisting essentially of (I) an aqueous solution of a water-solubleacid salt of an organosiloxane copolymer consisting essentially ofpolymeric units l) of the formula NH;CH2CHzNH(CHz)3SiY;O

where Y is selected from the group consisting of (OH) and (OR) radicalswhere R is an alkyl radical of less than 4 carbon atoms, and z is aninteger of from O to 2 inclusive, and and polymeric units (2) of theformula a)2 (O )mO References Cited UNITED STATES PATENTS 2,436,3042/1948 Johannson 88 2,754,311 7/1956 Elliot. 2,832,754 4/1958 Jex et a1.2,865,918 12/1958 Hurwitz et al 874 X 2,927,839 3/ 1960 Balley et a1. 882,971,864 2/1961 Speier.

FOREIGN PATENTS 553,033 12/1956 Belgium.

OTHER REFERENCES 1962 Technical Manual of the American Association ofTextile Chemists & Colorists; vol. XXXVIII, pages D76-D884, Pub. byAmer. Assoc. Textile Chemists & Colorists, 1962.

Textile World, vol. 109, No. 7, pp. 43-44.

DONALD LEVY, Primary Examiner U.S. Cl. X.R.

